Polyazo dyes



United States Patent Ice itiiiii :used as compounds of Formula H, thecoupling of the ,1 9, 9 resulting diazo compound with a compound ofFormula PQLYAZO DYES 111 can be effected in an acid or alkaline medium.When Heinz Wicki Allschwil Basel-Land Switzerland assignor t o SandozIZtd Basel, S Witzerland C uphng is carried out in an acid medium, e.g.an acetic 'v i 'd medium at pH values between 2 and 6 or preferably NoDrawing. Filed Feb. 25 1963 fler. No. 260 as 5 y o 0 Claims priority,appficafion Svvitzemmd, Fez 28, 17962, pd 4-5 and at temperaturesbetween .IO and +30 C.

2,455/62; r 5 19 2 929 2 or preferably O C., the diazo compound ispreferen- 6 Claims. (CI. Zed- 144) tially introduced into the 2-positionof the 1,3-dihydroxybenzene nucleus. It has been found that under theafore- This invention relates to polyazo dyes of the formula statedconditions scarcely more than 1 mole of such a CH N=N 2 011 no NH-OC V j4 -N=N--Nn) l 2.1-] p m 1 a (-N=NR)pi Y sea (I) wherein n represents theinteger 1 or 2, m, p and q each derivative of Formula II is capable ofcoupling with 1 represent the integer 1, 2 or 3, the sum m+p+q being 5,mole of a compound of Formula III. Hence it is possible a represents ahydrogen atom, a halogen atom (chlorine, to couple in alkaline medium 1mole of the resulting bromine), a substituted or unsubstituted alkyl oralkoxy disazo dye with 1 or 2 moles of a compound of Formula group (e.g.methyl, ethyl, methoxy, ethoxy), Y repre- II having at least onecarboxyl group, or with 1 or 2 sents a hydrogen atom or the sulfonicacid group, and R moles of a compound of the formula N=NR.

the radical of any desired diazo component, and in which In contrast tothe above reaction, the coupling in alkathe nuclei A and/ or B maycontain any substituents with line medium of a derivative of anaminodiphenylcarboxthe exception of sulfonic acid groups. ylic acid ofFormula II with a compound of Formula III These new dyes (I) canconveniently be prepared by causes the diazo compound to enter into the2- or 4- coupl-ing m moles of a diazotized amine of the formula positionof the 1,3-dihydroxybenzene nucleus or into the 7-posi-tion of thenaphthalene nucleus. In most cases @NHGNEE, the final product isheterogeneous. Under alkaline coni (H) d itions 1, 2 or 3 moles of aderivative of an aminodiand P- moles of y 03161 diazo COmPOHeHt with 1H1016 phenylearboxylic acid or 1 or 2 moles of a compound of of acoupling component f the formula the formula N=N--R can be coupled with1 mole of a compound of Formula 111 in any desired order.

These reactions are carried out in the pH region of 7.5

I N=N 2 OH to 12 or preferably between pH 8.5 and 9.5 and at tem- HO T Ij 4 40 peratures of 10 to C. or preferably between 1 0 C. and +:10 C. inan aqueous medium, to which an 7 organic solvent, e.g. pyridine or amixture of pyridine bases, may be added as required.

When aminodiphenylamine derivatives having no car- Y 503E m iboxyl groupare used as compounds of Formula II in the The preferred dyes are thosethat are obtained when the present P the coupling of the resulting diazonuclei A and/ or B of the amine of Formula H contain at pound a compoundof Formula? as coltducted least one cafibgxyl group. preferably in anand aqueous, e.g. acetic acid, medium, at

The radicals of the freely chosen diazo components PH Values of 2 tomore paartlculafly 4 to 5 and may be, for example, the diazo compoundsof substituted temPemtures of 7 to +30 or prelferably 045 orunsubstituted aminobenzenes, aminonaphthalenes, .lf.necessary.m thepresellqe of an organic Solvent aminohydroxynaphthalenes,aminonaphthalene SuIfOm-C pymdms or a mixture of pyridine bases. Underthe aforeacids, aminohydroxynaphthalene sulfonic acids, and statedconditions such compounds enter preferentially into aminon-aphthaleneswhich may be further substituted e.g. thfi zposition theladihydmxybenzene nucleus with chlorine or bromine arylamino, alkylaminoiandsub has been found that under the above conditions scarcely stimtedaminonaphth 31 ene S Diazo components which more than 1 mole of such acompound of Formula II can already contain one azo group can also beemployed. 'P coupled with mole Of a compound of Fflmmla HI; it

The following are named as examples of substituents is thereforepossible to couple 1 mole of the disazo dye f the aminobenzenfiszhalogen (chlorine, bromine), so formed with 1 or 2 moles of a compoundof Formula nitro, Sulfonic acid, carboxvl, alkyl such as methyl, ethyl Hhavmg at least 0116 CflPbOXYI g p or t 1 0r 2 moles etc., alkoxy such asmethoxy, ethoxy, substituted or unof a compound of the formula Thesereub tituted alkyl o 1ko lf jd alkyls lfo actions are performed inaqueous medium in the pH reamide, etc. gion of 7.5 to 12 or preferablyat pH 8.5 to 9.5 and in When derivatives of aminodiphenylcarboxylicacids are the temperature range of '10 to +30 C. or preferably to (3.,if necessary with the addition of an organic solvent, e.g. pyridine or amixture of pyridine bases. These compounds are preferentially introducedinto the 4- 'position of the 1,3-dihydroxybenzene nucleus or into the7-position of the naphthalene nucleus. The products are for the mostpart heterogeneous in constitution.

The new dyes are readily soluble in water, stable to acids and alkalis,and possess high afiinity for leathers manufactured with differenttannages, notably combination tanned leather. They give bright red toyellowish dark-brown shades. V T When in the present process nitroderivative of amino-' diphenylaminocarboxylic acids are used ascompounds of Formula II, valuable dyes are obtained which give yellowishdark-brown shades on leather having excellent fastness properties. Thesedyes are therefore of special interest for the dyeing and printing ofleather.

EXAMPLE 1 319 parts (1 mole) of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid are diazotized in the usual way and coupled with 110parts (1 mole) of 1,3-dihydroxybenzene in caustic alkaline solution; 318parts (1 mole) of 4- amino-2",4' -dinitro-6'-carboxydiphenylamine arediazotized in the usual way'with 69 parts of sodium nitrite inhydrochloric. acid solution. The diazo compound is cou- 4 r 7 compoundof p-nitraniline to yield a trisazo dye which is precipitated withcommon salt. It is obtained as a black powder which dissolves in waterwith a dark-olive green color and dyes leather in olive shades.

EXAMPLE 3 1 mole of the monoazo dye prepared as given in Exampie 1 fromdiazotized 1-amino-8-hydroxynaphthalene-3,6- disulfonic acid and1,3-dihydroxy benzene is coupled in acetic acid solution (pH 4-5) with274 parts (1 mole) of the diazo compound of4-amino-2,4'dinitrophenylamine. After the reaction the dye isprecipitated with common salt and dried. It is in the form of ared-broym powder which dyes leather in dark red-brownshades.

EXAMPLE 4 rakisazo dye is completely precipitated with commensalt V anddried to give a dark-brown powder which dyes leathpled with the monoazodye at pH 10. .On completion of the coupling reaction the dark greendisazo dye is coupled with a further 636, parts .(2 moles) of the diazocompound 4-amino-2',4' -dinitro-6-carboxydiphenylamino at a constant pHvalue of 8.5 maintained by dropwise addition 'of sodium hydroxidesolution. When coupling is finished common salt is added together with alittle hydrochloric acid to adjust the pH value to 7. The dye isprecipitated and isolatedas a dark brown'powder, which dies leather indark yellow-brown shades.

EXAMPLE 2.

The monoazo dye is prepared as described in Example 1 from diazotizedl-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 1,3-dihydroxybenzene, and 1 mole coupled in soda-alkaline solution at pH 10.5 with298 parts (1 mole) of the diazocompound of 4-amino-4'-nitrodiphenylamino-Z'-sulfonamide. On completion of couplingthe dark-green disazo dye so formed .is coupled in acetic acid solutionwith 138 parts (1 mole) of the diazo 'er in deep dark-brown shadeshaving very good fastness properties.

. EXAMPLE 5.

V nitro-2sulfo-diphenylamine is slowly added at pH 9.5-10.

On completion of this coupling reaction the final tetrakisazo dye isprecipitated with common salt and dried. It is obtained as a black-brownpowder which dyes leather in dark yellow-brown shades.

The following Table I contains particulars of further dyes which can beobtained according to the procedures of Examples 3, 4 and 5. In column Ithebasic scheme of the dye of Formula 111 is shown and in columns 11, HIand IV the further components are enumerated which are suitable for thesynthesis of dyes of Formula I. In column V the shade of the dyeing onleather is noted. The diazo compounds listed in column 11 can be coupledin 'acid medium preferably in the 2-position of the 1,3-di

hydroxybenzene nucleus.

Table 1 Ex. N0. r

6 1-amino-8-hydroxynaphtha1ene-3,6-disulfonic acid 1,4-amino-2,4-dim'trol-amino-emethoxy- Dark yellow- 3-dihydroxybenzene.dlphenylamine. benzene. brown. 7 do l-amlnobenzenek Dark redsulfonicacid. brown. 8 o l-aminoknitroben- Dark-brown.

zene. 9' l-aminoi-uitroben- Dark redzene-2-su1fonic acid. brown. 10 dol-amino-Z-methylben- Do.

' zene--sulfonie acid. 11; J -do l-amino-naphthalene- Do.

6-su1fonic acid. l2 d0 .do Laminonaphthalene- Do.

4-sulfonic acid. do d0 4-amlno-1,1-azoben- .-l Do.

In Table 2 below details are given of further dyes V which can beobtained using the procedures of Examples 1 and 2. In column I the basicscheme of the dye of Formula III is shown and in columns II, III and 1Vfurther components are enumerated which are suitable for the synthesisof dyes of Formula 1. Column V gives the shade of the dyeing on leather.7

Table 1Continued Ex. (I) A V) V i ,N tt u .7 t

4-amino-2-,4-dinitrol-amino-4-methoxya. Brown;

I diphenylamine. benzene. r

36- do I-aminQA-methoXy- Do.

a r benzene. HOfim-SCQI Q 0U V 0H on NHOCQ N=N fin e. l l A CH3 HO HOaS-s0n1 7 38... OH do l-aminoA-methoxy- D0.

[ benzene.

CH3 HO' 7 H038 SO3H 89-- OH NHOC N=If D0.

' OCH:

H038 I 303B 7 1 is 7 HO A 45---" on I IH oo N=III Do.

. VCZHS t e t t t w n SOaH SO3H l 0E 1-|IH-oo =1Tr do an OOZH5 9 SOsHSOaH V L The diazo compounds listed in column 11' can be coupled in anacid medium preferably in the 2-position of the 1,3-dihydroxybenzenenucleus when they contain a carboxyl group. The diazo compounds listedin columns 11, III andrIV can be coupled in an alkaline medium in the 2-or 4-position of the 1,3-dihydroxybenzene nucleus or in the 7-positionof the naphthalene nucleus.

13 DYEING EXAMPLE A 100 parts of freshly tanned, neutralized chromegrain leather are entered into a bath of 250 parts of water at 65 and 1part of the dye of Example 1 in a drum dyeing machine. The leather isdrummed for 30 minutes. 2 parts of an anionic fat liquor based onsulfonated train oil are added to the bath and drumming continued for 30minutes. The leather is dried and finished in the usual way. It is dyedto a level, dark yellow-brown shade.

DYEING EXAMPLE B 100 parts of calf suede leather are wetted back for 4hours in a bath of 1000 parts of water and 2 parts of O O H H O as 14*DYEING EXAMPLE 0 100 parts of chrome lamb leather are drummed forminutes in a bath of 1000 parts of water at 10 parts of the dye ofExample 3, and 1.5 parts of an anionic sperm oil emulsion. Subsequently,5 parts of formic acid are added slowly for exhaustion and drummingcontinued for 30 minutes to obtain complete fixation of the dyeing. Theleather is dried and finished in the usual way. It is dyed in a leveldark redbrown shade.

DYEING EXAMPLE D a A solution is prepared with 20parts of the dye ofExample 4, 847 parts of water, parts of ethyl glycol and 3 parts of 85%formic acid. It is applied to the grain side of a bufied, combinationtanned side leather by spraying, curtain coating or with a plush pad,and the dyeing dried under mild conditions. In this way a level surfacedyeing is produced which serves as a ground for subsequent finishingwith opaque colored pigments and synthetic resin binders.

Formulae of representative dyes of the foregoing examples are asfollows:

EXAMPLE 1 l 2 f I O O SOaH (JOOH EXAMPLE 4 EXAMPLE 5 -S 0 all A mixtureof two polyazo dyes of the formulae II N SOaH and on VN=N SOsH HOzS N=NHOaS S0311 7 EXAMPLE 2s g 7 A mixtnreof two polyazo dyes of the formulaeT r V 0H NV=N 4 01 1 OH No,

soar: S03H No, a V

V V V I 1103s I aild V N O 3 and en ,N=N-C -0H son Having thus disclosedthe-invention what I claim is: 1. Polyazo dye of the formula V t 0H V IV l I 2 m (NH 00 @F- N=N-C NH-x)m 1/ 7 a hydrogen, halogen, lower alkyl,lower alkoxy, is a member selected from the group consisting of COOHhydrogen and a sulfonic acid group, 75 a (I) (m wherein X is a memberselected from the group consisting of n is one of the integers 1 and 2the moieties m, p and q each is one of the integers 1, 2 and 3, the 70 a7 sum m+p+q being 5, V I g r a is a member selected from the groupconsisting of 0 7 l 1 diphenylamino which contains moiety I beingattached to the 2-position of the resorcin nucleus and diphenylaminowhich contains moiety H being attached to one of the numbered freepositions in the aforesaid formula, and

R is the radical of a diazo component selected from 5 the groupconsisting of diazotized 4-amino-2',4-dinitro-6-carboxydiphenylamine,l-aminonaphthalene-sulfonic acid, 2-aminonaphtha1ene-disulfonic acid,4-amino-4-nitro-2'-sulfo-diphenylamine, 1Q I-amino-lower alkoxy-benzene,

l-amino-lower alkoXy-benzene-sulfonic-acid,1-aminobenzene-monosulfonic-acid, l-amino-mononitrobenzene,1-amino-mononitrobenzene-sulfonic-acid,

2. The polyazo dye of the formula C O OH H0 8- OH N=N OH (50011 I N07 iSO;H

3. The polyazo dye of the formula on I 4. The mixture of two polyazodyes of the formulae OH N=NI SOaH H038 and HOzS- =N OH i N- S0311 S03115. The mixture of two polyazo dyes of the formulae a W0 RH OZNQHMQMP Q-SO:H

SOaH HOaS- I RH r Q- Q- 7 19 y and 7'' 7V V V 7:7: i M

NO: (I) )3 1YT=N 0H 7 7 SOsH 6. The mixture of twofpolyazo dyes of theformulae and V References Cited by the Examiner UNITED STATES PATENTS2,061,545 1 1/36 Bosshart et a1 260166 XR 2,758,109 8/56 Huss et a1260--169 2,830,979 4/58- Geebel et a1. 260166 XR CHARLES B. PARKER,Primary Examiner.

1. POLYAZO DYE OF THE FORMULA